Development of carbon-carbon sigma-bond activation with rhodium catalysts.

Abstract

ABSTRACT OF THE DISSERTATION: Development of Carbon–Carbon Sigma–Bond Activation with Rhodium Catalysts. Chapter 1. This chapter provides a review of the chemistry of metal catalyzed reactions involving normally unreactive sigma-bonds. Literature examples for a variety of methods to activate C–C and C–H sigma-bonds are discussed in detail. Particularly the preliminary work of Suggs and Jun in this field is presented. Chapter 2. Presented herein is the development of an intermolecular and chemoselective method for C–C and C–H sigma-bond activation based on rhodium catalyst and solvent. The synthesis of substrates and optimization is presented. The results are given for a variety of substrate ketones and alkenes. Finally, a discussion of the mechanism is presented. Chapter 3. Presented herein is the development of an intramolecular carboacylation of alkynes with activated C–C sigmabonds with rhodium catalysts. The synthesis of the substrates and optimization is presented. Results are presented with a number of substrates with various electronic groups. Mechanistic considerations are presented as well. Chapter 4. Presented herein are the studies toward C–C sigmabond activation with an organic co-catalyst. The synthesis of substrates and a number of investigations with them are presented. Finally, a discussion of future work in this project is presented.